KR20150085593A - Cleaning composition for electronic material - Google Patents

Abstract

The present invention relates to a cleaning composition for an electronic material having excellent corrosion prevention effect for a metal film or a metal wire by including at least one imidazole derivative compound, a base compound, and water selected among a group composed of 1,2-dimethylimidazole, 1-isopropyl-2-methyl imidazole, and 1-benzyl-2-methyl imidazole.

Description

{CLEANING COMPOSITION FOR ELECTRONIC MATERIAL}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning liquid composition for electronic materials, and more particularly, to a composition that can be used for removal of contaminants generated during electronic material production and peeling of photoresist.

An electronic material used for a semiconductor device, a liquid crystal display such as a FPD, etc. is manufactured through various processes, and specific examples thereof include a film forming process, an exposure process, a wiring etching process, and the like. Particles having a size of 1 탆 or less are adhered to cause contamination of the substrate. When the following process steps are carried out with such contaminants adhering to the substrate, pinholes, pits, wirings, and bridges of the film are generated, thereby significantly decreasing the production yield of products. Therefore, cleaning for removing such contaminants is carried out between respective processes, and various cleaning liquids have been introduced for this purpose.

Japanese Laid-Open Patent No. 2002-184743 discloses a composition for removing polymeric materials from a substrate, comprising at least one polyhydric alcohol, water, at least one water-miscible amine, and at least one polar solvent. However, the composition has the disadvantage of causing corrosion of the metal wiring.

US Patent Application No. 10-2001-0015565 discloses a composition for removing polymeric materials from a substrate, comprising a polyol compound, a glycol ether, at least 5 weight percent water, a fluoride salt, and an additive. However, since the composition uses a large amount of polyol, the rinsing property when rinsed with water after use of the cleaning liquid deteriorates, and the fluoride salt contained in the composition causes a problem of precipitation during long-term use and also causes a problem of corrosion of the metal wiring .

HL Patent Application No. 10-2006-0076073 discloses a composition comprising at least one polyol compound, at least one glycol ether solvent, N-methylpyrrolidone, and at least one corrosion inhibitor, which is substantially water-free , A composition for removing polymeric materials from a substrate. However, the use of a large amount of an organic solvent is not environmentally preferable, and the corrosion resistance of the metal wiring is insufficient.

Japanese Patent Laid-Open No. 2002-184743 Korean Patent Application No. 10-2001-0015565 Korean Patent Application No. 10-2006-0076073

The present invention has an excellent ability to remove organic contaminants or particles that contaminate a glass substrate or a metal film and a peeling ability of a photoresist existing in a glass substrate or a metal film in a process of manufacturing an electronic material or the like, And an object of the present invention is to provide such an excellent cleaning liquid composition for electronic materials.

1. at least one imidazole derivative compound selected from the group consisting of 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole and 1-benzyl-2-methylimidazole; A basic compound which is at least one of an alkylammonium hydroxide compound having 1 to 20 carbon atoms and an amine compound; And water.

2. The composition of claim 1, wherein the alkylammonium hydroxide compound having 1 to 20 carbon atoms is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Wherein the cleaning liquid composition is at least one selected from the group consisting of a surfactant, a surfactant, and a surfactant.

3. The method of claim 1, wherein the amine compound is selected from the group consisting of monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, At least one alkanol selected from the group consisting of diethylaminoethanol, nitrilotriethanol, 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine and dibutanolamine Amine. ≪ / RTI >

4. The composition of claim 1 wherein said amine compound is selected from the group consisting of hydroxylamine, diethylhydroxylamine, N- (benzyloxycarbonyl) hydroxylamine, and o- (4-nitrobenzoyl) Wherein the organic solvent is at least one hydroxylamine selected from the group consisting of o- (4-nitrobenzoyl) hydroxylamine).

5. The cleaning liquid composition for electronic materials according to 1 above, which comprises 0.01 to 10% by weight of the imidazole derivative compound, 5 to 30% by weight of the basic compound and water in a residual amount.

6. The cleaning liquid composition for electronic materials according to 5 above, further comprising 0.01 to 10% by weight of a fluorinated compound.

7. The process of claim 6, wherein the fluorinated compound is selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium bifluoride, tetrabutylammonium fluoride, tetrabutylammonium bifluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, Wherein the cleaning liquid composition is at least one selected from the group consisting of trimethylammonium fluoride and trimethylammonium fluoride.

8. The cleaning liquid composition for electronic materials according to any one of 5 to 7 above, further comprising 1 to 50% by weight of a water-soluble organic solvent.

9. The composition of claim 8, wherein the water soluble organic solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether , Polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-methylpyrrolidone (NMP), N-ethylpyrrolidone , 1,3-di Dimethyl sulfoxide, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, tributyl phosphate, dimethyl carbonate, dimethyl carbonate, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, At least one selected from the group consisting of methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N- Wherein the cleaning liquid composition for electronic materials is one.

INDUSTRIAL APPLICABILITY The cleaning liquid composition for electronic materials of the present invention is excellent in the ability to remove organic contaminants and particles present on a glass substrate such as an electronic material or on the surface of a metal film and is useful for peeling off a photoresist existing on a glass substrate or a metal film surface have.

Further, the cleaning liquid composition for electronic materials of the present invention is excellent in corrosion prevention effect against metal film formed on a substrate, metal wiring and the like. Particularly, the corrosion inhibiting effect is excellent for transition metals such as Cu, Co, Ru, Pd, W and Ti, alloys including metal, metal oxides, metal nitrides, silicon compounds and silicon oxides.

The present invention relates to at least one imidazole derivative compound selected from the group consisting of 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole and 1-benzyl- And water so as to provide a cleaning liquid composition for electronic materials excellent in corrosion resistance to metal film or metal wiring.

Hereinafter, the present invention will be described in more detail.

The cleaning liquid composition for electronic materials of the present invention includes an imidazole derivative compound, a basic compound and water.

The imidazole derivative compound according to the present invention is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole and 1-benzyl- .

The specific imidazole derivative compound according to the present invention is excellent in corrosion inhibition effect against a metal used for a metal film, a metal wiring, etc. used for a semiconductor process or the like.

The imidazole derivative compound is preferably contained in an amount of 0.01 to 10% by weight based on the total weight of the composition. In this range, the corrosion prevention effect of the metal may be most excellent. If it is contained in an amount exceeding the above range, the detergency and peelability may decrease, and the etching amount of some metals may increase.

The basic compound according to the present invention functions to decompose or dissolve the impurities remaining on the surface of the article to be cleaned. The basic compound according to the present invention may include at least one of an alkylammonium hydroxide compound having 1 to 20 carbon atoms and an amine compound.

More specific examples of the alkylammonium hydroxide compounds having 1 to 20 carbon atoms include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and cholinehydroxide. At least one selected from the group consisting of

The amine compound may be at least one of an alkanolamine and a hydroxylamine.

More specific examples of the alkanolamine include monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, At least one selected from the group consisting of aminoethanol, nitrilotriethanol, 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine and dibutanolamine.

More specific examples of the hydroxylamine include hydroxylamine, diethylhydroxylamine, N- (benzyloxycarbonyl) hydroxylamine, and o- (4-nitrobenzoyl) hydroxylamine ( o- (4-nitrobenzoyl) hydroxylamine).

The basic compound according to the present invention is preferably contained in an amount of 5 to 30% by weight based on the total weight of the composition. In the above range, the washing power and the peeling ability are most excellent. If it is contained in an amount exceeding the above range, the detergency and peelability may decrease, and the etching amount of some metals may increase.

Water according to the present invention dissolves each component and controls the overall composition, and the balance of the total composition is occupied by water. Preferably, the components are adjusted to have the aforementioned content ranges.

Water is not particularly limited, but it is preferable to use deionized water having a resistivity value of 18 M? 占 cm m or more as water for semiconductor processing.

Alternatively, the cleaning liquid composition of the present invention may further comprise a fluorinated compound. The fluorine compound functions to decompose the impurities remaining on the surface of the object to be cleaned together with the basic compound.

Specific examples of fluorine compounds include hydrofluoric acid such as hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, Rides, etc. may be used alone or in combination of two or more, but the present invention is not limited thereto.

The fluorine compound may be contained in an amount of 0.01 to 10% by weight based on the total weight of the composition. In the above range, the washing power and the peeling ability are most excellent. If it is contained in an amount exceeding the above range, the detergency and peelability may decrease, and the etching amount of some metals may increase.

Alternatively, the cleaning liquid composition of the present invention may further comprise a water-soluble organic solvent. The water-soluble organic solvent functions to dissolve or disperse the impurities together with water.

Specific examples of the water-soluble organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Ethylene glycol monomethyl ether, glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol Propylene glycol monomethyl ether acetate, N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 1, 2-butanediol monomethyl ether, 3-di Imidazolidinone, gamma -butyrolactone, dimethylsulfoxide (DMSO), sulfolane, triethylphosphate, tributylphosphate, dimethyl carbonate, dimethyl carbonate, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, etc., Mix more than one species.

The water-soluble organic solvent may be contained in an amount of 1 to 50% by weight based on the total weight of the composition. The detergency and peeling ability may be the most excellent in the above range, and if it is contained in an amount exceeding the above range, the detergency and peeling ability may be decreased and there is a possibility that some components are precipitated.

The cleaning liquid composition for electronic materials of the present invention may further contain additives known in the art as needed. Such an additive may further include, for example, a surfactant, a chelating agent, and the like, but is not limited thereto.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example

A cleaning liquid composition was prepared according to the composition shown in Table 1 below (unit weight%).

Basic compound Fluorine compound water
(H ₂ O) Organic solvent Corrosion inhibitor TMAH TBAH CH TEA HA DMSO IZ MPIZ MBIZ DMIZ IPMIZ BMIZ Example 1 23 73 4 Example 2 17 12 69 2 Example 3 17 8 5 41 25 4 Example 4 15 3 80 2 Example 5 30 68 2 Example 6 22 8 5 63 2 Example 7 20 8 2 68 2 Example 8 20 3 45 30 2 Example 9 32 64 4 Example 10 24 12 2 58 4 Example 11 25 8 8 15 40 4 Example 12 24 3 71 2 Example 13 22 12 62 4 Example 14 10 15 2 71 2 Example 15 8 15 2 55 18 2 Example 16 14 5 3 66 12 Comparative Example 1 18 80 2 Comparative Example 2 18 5 75 2 Comparative Example 3 15 8 75 2 Comparative Example 4 24 72 4 Comparative Example 5 22 5 39 30 4 Comparative Example 6 20 12 63 5 Comparative Example 7 25 73 2 Comparative Example 8 20 8 70 2 Comparative Example 9 18 5 73 4 Comparative Example 10 20 2 44 30 4
- TMAH: tetramethylammonium hydroxide
- TBAH: tetrabutylammonium hydroxide
- CH: choline hydroxide
- TEA: triethylamine
- HA: hydroxylamine
- Fluorocarbon compound: Ammonium fluoride
- DMSO: dimethylsulfoxide
- IZ: imidazole
- MPIZ: 2-mercaptobenzimidazole
- MBIZ: 4-methyl-2-phenylimidazole
- IPMIZ: 1-isopropyl-2-methylimidazole
- BMIZ: 1-benzyl-2-methylimidazole

Test Example

1. Evaluation of cleaning power

The wafer substrate on which the organic / inorganic residue was present was cut into a size of 2 cm x 2 cm, and then immersed in the cleaning liquid compositions of the above-described Examples and Comparative Examples for 2 minutes. The temperature of the cleaning liquid was 70 캜. After immersion, rinsing was performed for 1 minute using deionized water, and the substrate was completely dried.

Thereafter, the ratios of the residues remaining after the cleaning with respect to the residues before cleaning were evaluated using SEM according to the following evaluation criteria, and the results are shown in Tables 2 and 3 below.

 [Evaluation standard]

◎: Less than 0 ~ 5%

○: 5% or more to less than 10%

Δ: 10% or more to less than 30%

×: not less than 30% and not more than 100%

2. Corrosion resistance  evaluation

The silicon wafer substrate coated with the metal film to be evaluated in a thickness of 500 Å was cut into a size of 2 cm × 2 cm, and then immersed in the cleaning liquids of the above-described Examples and Comparative Examples for 10 minutes, respectively. At this time, the temperature of the cleaning liquid was 70 占 폚. After immersion, the substrate and the substrate were rinsed for 1 minute by using the above and deionized water.

The thickness of the metal film to be evaluated applied to the wafer substrate was measured using an SEM before and after the immersion, and the etch rates were measured from the change in thickness, and the evaluations thereof are shown in Tables 2 and 3 below.

Cleaning power Etching speed (Å / min) W Poly-Si SiOx Example-1 ○ 0.0 4.5 0.0 Example-2 ○ 0.0 5.5 0.0 Example-3 ◎ 0.0 0.0 0.0 Example-4 ◎ 0.0 8.0 0.0 Example 5 ○ 0.0 3.5 0.0 Example-6 ◎ 0.0 2.0 0.0 Example-7 ◎ 0.0 7.0 0.0 Example-8 ◎ 0.0 5.0 0.0 Example-9 ○ 0.0 2.0 0.0 Example-10 ◎ 0.0 1.5 0.0 Example-11 ◎ 0.0 0.0 0.0 Example-12 ◎ 0.0 0.0 0.0 Example-13 ◎ 0.0 2.5 0.0 Example-14 ◎ 0.0 0.0 0.0 Example-15 ◎ 0.0 5.5 0.0 Example-16 ○ 2.5 12.0 1.5

Cleaning power Etching speed (Å / min) W Poly-Si SiOx Comparative Example 1 ○ 15.0 74.5 0.0 Comparative Example 2 ○ 11.0 60.0 0.0 Comparative Example 3 ◎ 11.0 70.0 0.0 Comparative Example 4 ○ 16.5 95.5 0.0 Comparative Example 5 ○ 13.0 79.5 0.0 Comparative Example 6 ◎ 15.0 80.0 0.0 Comparative Example-7 ○ 12.0 54.5 0.0 Comparative Example-8 ○ 13.5 55.0 0.0 Comparative Example-9 ◎ 13.0 55.0 0.0 Comparative Example-10 ◎ 18.0 104.5 3.5

Referring to Table 2 and Table 3, it can be confirmed that the etching amount of the metal film is remarkably low in the examples as compared with the comparative examples. Particularly, in the comparative examples, although the cleaning power was sufficiently exhibited, it was confirmed that the degree of etching of the metal film was large.

On the other hand, in the case of Example 16 in which 1-isopropyl-2-methylimidazole was slightly added, it was confirmed that the damping force against the metal film was slightly lowered.

Claims (9)

At least one imidazole derivative compound selected from the group consisting of 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole and 1-benzyl-2-methylimidazole;
A basic compound which is at least one of an alkylammonium hydroxide compound having 1 to 20 carbon atoms and an amine compound; And
A cleaning liquid composition for electronic materials comprising water.
The method of claim 1, wherein the alkylammonium hydroxide compound having 1 to 20 carbon atoms is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and cholinehydroxide Wherein the cleaning liquid composition is at least one selected from the group consisting of:
[Claim 2] The method according to claim 1, wherein the amine compound is selected from the group consisting of monoethanolamine, diethanolamine, 2- aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, At least one alkanolamine selected from the group consisting of ethylaminoethanol, nitrilotriethanol, 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine and dibutanolamine , A cleaning liquid composition for electronic materials.
The amine compound according to claim 1, wherein the amine compound is selected from the group consisting of hydroxylamine, diethylhydroxylamine, N- (benzyloxycarbonyl) hydroxylamine and o- (4-nitrobenzoyl) hydroxylamine (o- (4-nitrobenzoyl) hydroxylamine). < / RTI >
The cleaning liquid composition for electronic materials according to claim 1, which comprises 0.01 to 10% by weight of the imidazole derivative compound, 5 to 30% by weight of the basic compound and water in a remaining amount.
The cleaning liquid composition for electronic materials according to claim 5, further comprising 0.01 to 10% by weight of a fluorinated compound.
7. The method of claim 6, wherein the fluorinated compound is selected from the group consisting of hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrobromic acid, hydrobromic acid, Wherein the cleaning liquid composition is at least one selected from the group consisting of fluoride, fluoride, and fluoride.
The cleaning liquid composition for electronic materials according to any one of claims 5 to 7, further comprising 1 to 50% by weight of a water-soluble organic solvent.
[Claim 8] The method of claim 8, wherein the water-soluble organic solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 1 , 3- Dimethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, gamma -butyrolactone, dimethylsulfoxide (DMSO), sulfolane, triethylphosphate, tributylphosphate, dimethylcarbonate, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, At least one selected from the group consisting of methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N- Wherein the cleaning liquid composition for electronic materials is one.